New dyestuffs of the anthraquinone series containing a chlorotriazine substituent



United States Patent 3,133,921 NEW DYESTUFFS OF THE ANTHRAQUINUNE SERIESCONTAINING A CHLOROTRIAZINE SUBSTITUENT Jakob Brassel and Max Staeuble,Basel, Switzerland, assignors to Ciba Corporation, a corporation ofDelaware No Drawing. Filed Sept. 22, 1961, Ser. No. 139,887 Claimspriority, application Switzerland Sept. 12, 1956 3 Claims. (Cl. 260-249)This is a continuation-impart of our application Serial No. 682,599filed September 9, 1957 (now abandoned).

This invention provides new water-soluble dyestuffs of the anthraquinoneseries which contain a monohalogentriazine radical. These new dyestuffscontain at least two acid groups imparting solubility in water andcorrespond to the general formula wherein m and n each represents awhole positive number up to and including 2, R represents a phenyleneradical (including the sulfophenylene radicals) and Y is a memberselected from the group consisting of the sulfophenoxy, sulfophenylaminoand sulfonaphthylamino groups. 7

These dyestuffs are made in accordance with the invention by condensing2:4:6-trich1oro-l13:5-triazine, on the one hand, with a water-solubleanthraquinone dyestulf of the formula and, on the other, with aphenolsulfonic acid or with an aromatic amine containing at least onesulfonic acid group, for example, with an aminobenzene sulfonic acid oraminonaphthalene monoor di-sulfonic acid, the condensation being carriedout in such manner that a secondary condensation product is obtainedwhich contains a halogen atom bound to the triazine nucleus.

As examples of anthraquinone dyestuffs which can be used as startingmaterials in the process of this invention there may be mentioned thefollowing:

1-amino-4-(3'- or -4-aminophenylamino) -anthraquinone- 2-sulfonic acid,

1 amino-4-(4'-aminophenylamino)-anthraquinone-2'- or 3'-sulfonic acid,

1-amino-4-(3-amino-6-methylphenyl-amino)-anthraquinone-2-sulfonic acid,

1-amino-4- 3 -amino-phenylamino) -anthraquinone-4- sulfonic acid,

l-amino-4- 4-aminophenylamino -anthraquinone-2 2'- or 2:3 -disulfonicacid,

l-amino-4-( 3 -aminophenyl amino -anthraquinone-2 4'- disulfonic acid,

1-amino-4- 3 '-aminophenylamino) -anthraquinone-2: 3

5-, 2:3:6-, 2:3':7- or 2:3z8-trisulfonic acid,

1-amino-4-(4-an1inophenylamino) -anthraquinone-2 2':

S-trisulfonic acid,

l-amino-4- 3 '-aminophenylamino) -anthraquinone-2 4':

S-trisulfonic acid,

1-amino-4- [4- 4-aminophenyl -phenylamino -anthraquinone-2 3"-disulfonicacid,

l-amino-4- [4'-(4-aminophenyla1o)phenylamino] -anthraquinone-Z 2S-trisulfonic acid,

1-amino-4- (4-amino-3 -carboxyphenylamino) -anthraquinone-2 5-disulfonic acid,

l-amino-4- 3 '-aminophenylamino) -anthraquinone-2 5 4-trisulfonic acid,

and also 1:5-dioxy-4 8-diaminoanthraquinone-2 6-disulfonic acid and1:4-diaminoanthraquinone-2-sulfonic acid.

In the process of this invention, for example, one molecular proportionof cyanuric chloride may be reacted with one molecular proportion of aphenolsulfonic acid or with one molecular proportion of an aminobenzenesulfonic acid. As such compounds there may be mentioned ortho-, metaorpara-aminobenzene sulfonic acid and l-aminobenzene-Z:S-disulfonic acid,aminonaphthalene sulfonic acids, such as 1-aminonaphthalene-4-, -5-, -6-or -7-sulfonic acid, 2-aminonaphthalene-4-, -6- or -8- sulfonic acid,1-aminonaphthalene-3:6-disulfonic acid, 2- aminonaphthalene-4:8-, 5:7-or 6:8-disulfonic acid.

The condensation of the trihalogen-triazines with the compoundsmentioned above to form primary condensa tion products is advantageouslycarried out in the presence of an acid-binding agent, such as sodiumacetate, sodium hydroxide or sodium carbonate, and under conditions suchthat two exchangeable halogen atoms remain in the product obtained, thatis to say, for example, in an organic solvent or at a relatively lowtemperature in an aqueous medium. The primary condensation products soobtained are further condensed to secondary condensation productsadvantageously at a somewhat raised temperature, for example, within therange of 30-90 C., and advantageously 5580 C. In this manner thecondensation proceeds more rapidly and more completely than at lowertemperatures, and it is surprising that the third chlorine atom of thecyanuric chloride used is not attacked.

The products of the Formula 1 are new. They are valuable dyestuifs whichare suitable for dyeing or printing a very wide variety of materials,especially polyhy droxylated materials of fibrous structure such ascellulose-containing substances, and also synthetic fibers, for example,of regenerated cellulose or viscose, or natural materials, for example,linen, cellulose or above all cotton. They are suitable for dyeing bythe so-called direct dyeing method and also by the pad dyeing method,especially from aqueous alkaline solutions, which may have a highconcentration of a salt, for example, by the process in which thedyestuiis are fixed on the material to be dyed by means of an acidbinding agent in the warm.

Notwithstanding that they contain a labile halogenatom the dyestuiis ofthis invention can be isolated without losing their valuable properties,and worked up into useful dry dyestuff preparations. They areadvantageously isolated by salting out and filtration. The dyestuffswhich have been filtered olf may be dried, if desired, after theaddition of diluents. It is of advantage to carry out the drying at nottoo high a temperature and under reduced pressure. In some cases drypreparations can be prepared in accordance with the invention by spraydrying the mixture resulting from the preparation of the dyestuif, thatis to say, without first separating the dyestulf.

In this manner new valuable dry preparations are obtained which aresuitable for the preparation of stock solutions or dyebaths, and, ifdesired, also printing pastes.

Dyeings produced on cellulose-containing fibers with the new dyestuffsof the Formula 1 are usually distinguished by the purity of their tints,their good fastness to chlorine and light and especially by theirexcellent fastness to washing.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relationshipof parts by weight to parts by volume being the same as that of thekilogram to the liter:

Example 1 NH; 01 H I I C 0 t NH- -NH- \o/ 1 K O 0 NH S0 11 100 parts ofice are added to 20 parts of cyanuric chloride in 80 parts of acetone.To the suspension of cyanuric chloride so obtained there is added asolution, cooled to 0 C., of 32.7 parts of the disodium salt ofl-aminobenzene-Z:5-di-sulfonic acid in 330 parts of water. To themixture there are introduced dropwise in the course of 2 hours 55 partsby volume of a 2 N-solution of sodium carbonate, the temperature beingmaintained at 24 C. by the external cooling. There is obtained a clearsolution of the condensation product of equirnolecular quantities ofcyanuric chloride and l-aminobenzene- 2:5-disulfonic acid, which may, ifnecessary, be filtered to remove small amounts of undissolvedimpurities.

The solution so obtained is added without delay to a solution having atemperature of 40 C. of 43.1 parts of the sodium salt of1-amino-4-(3'-aminophenylamino)- anthraquinone 2-sulfonic acid and 5.3parts of sodium carbonate in 2000 parts of water. The reaction mixtureis heated to 35-40" C. and stirred for one hour at that temperature. Thedyestuif so obtained is precipitated by the addition of sodium chloride,filtered off and dried in vacuo at 90 C. It is a dark colored substancewhich dyes cotton in the manner described below reddish blue tints whichare fast to light and washing.

1 part of the dyestuff is dissolved in 100 parts of water. A fabric ofstaple fibers of regenerated cellulose as impregnated in the resultingsolution so that its weight increase is 75%, and then the fabric isdried. The fabric is then impregnated with a solution at 20 C. whichcontains, per liter, grams of sodium hydroxide and 300 grams of sodiumchloride, the fabric is squeezed to a Weight increase of 75%, and thedyeing is steamed for 60 seconds at 100-101 C., rinsed, treated in asodium bicarbonate solution of 0.5% strength, rinsed, soaped for hour ina boiling solution of 0.3% strength of a nonionic detergent, rinsed anddried.

If the steaming operation is omitted practically the whole of thedyestutf is washed out during the soaping operation.

A similar good result is obtained by using a cotton fabric, instead of afabric of staple fibers of regenerated cellulose.

Similar dyestuffs which dye cotton and regenerated cellulose the tintsgiven in column III of the following table are obtained in the aboveexample by using, instead of 1-amino-4 3 '-aminophenylamino-anthaquinone-2-sulfonic acid, equimolecular quantities of the startingdyestuffs given in column II:

0 NH, (II) 1 SO3H Reddish blue.

7 \C/ 1TH on.

H 0 0 ii 1 o 2 -s0nr Do.

\C/ ITIIL-C H NH; 0 3 -so3rr Blue.

\/ ll 0 I IHNI-I 0 NH, Il 4 -so3r1 D0.

II 0 NH- NH 0 11 u r 0 5 s0.rr D0.

II o NHNH-CHa 0 NH; y 6 -so.n Do.

l 30.11 t r C 7 -s0 1r D0.

\O/ ITIHZ ll 0 i trr- -Cl t o s so3rr Do.

l] l o NH-O-NI-Iz ooorr Example 2 100 parts of ice are added to asolution of 20 parts of cyanuric chloride in 80 parts of acetone. Theresulting suspension of cyanuric chloride is added to a solution, 5cooled to 0 C., of 21.5 parts of the sodium salt of 1-aminobenzene-3-sulfonic acid in 330 parts of Water. To the mixture areadded dropwise in the course of 5 minutes 55 parts by volume of a 2N-solution of sodium charbonate, the temperature being maintained below5 C. by external cooling. There is obtained a clear solution of thecondensation product of equimolecular quantities of cyanuric chlorideand 1-amino-benzene-3-sulfonic acid, and, if necessary, small amounts ofundissolved impurities may be filtered off.

The solution so obtained is added without delay to a solution at 40 C.of 53.3 parts of the disodium salt of 1 amino4-(4'-aminophenylamino)-2:3-disulfonic acid and 5.3 parts of sodiumcarbonate in 1000 parts of water. The reaction mixture is heated to40-50 C. and stirred for 2 hours at that temperature. The dyestuff soobtained is precipitated by the addition of sodium chloride, filteredoif and dried in vacuo at 90 C. There is obtained a dark coloredsubstance which dyes cotton and regenerated cellulose by the processdescribed in Example 1 blue tints Which are fast to washing and light.

Similar dyestuifs, which dye cotton and regenerated cellulose bluetints, are obtained by using in this example, instead of1-amino-4-(4-aminophenylamino)-anthraquinone-2:3Gdisulfonic acid thecompounds named in column II of the following table, and by usinginstead of l-aminobenzene-S-sulfonic acid, the corresponding quantity ofthe compounds given in column III in the form of their neutral sodiumsalts.

t IYTH: 17H 0 1 -SO3H Reddish blue.

I f l IfH-OH: s03rr H038 0 NH@ 0 NH, -z II I v o 2 S 03H Greenish blue.

s0 H \C/ 3 1] 1103s 0 l IHNHC H 1103s 17m ITIHZ o 3 -SO;H Blue.

s H T 03 t F T 0 4 SO3H Greenlsh blue.

HO3S \C/ 1 ii I IHO-NH sour 6 T u o 5 -S03H S03H Do.

I ii l IH-NH CH3 1 SOBH l u I 0 s SO3H Do.

t 1 H038 o NEG-NH, s03];

I III IV I? i o 7 -s0311 H30 Grccnish blue.

S 0 3H Ii 0 NH NH2 I s 0311 I i T o s SO3H DO.

0 H 0 ss- S 0 311 II 0 O- S 0311 0 NH, (II: I 9 -s0lH HiN D0.

\O/ SO3H I II 1103s 0 NHC -NH2 I S 03H lTIHz T 2 0 o 10 S 3 Blue.

\C O I S 0311 NH NH1 w l c 0 11 SO3H Do.

\C O S 03H NE[ NH;

H 0 as -S 0 3H IIQ'HQ ITIHQ o 0 12 s03H Do.

I I NH -NH, s 03H noas -SO3H The 1-amino-4-(3'-aminophenylamino)-anthraquinone- 2:4:6'-trisulfonic acid used for making the dyes Nos. 11and 12 of the table can be obtained by sulfonation of the (1 amino(3'-aminophenylamino) -anthraquinone-2-sul fonic acid with forming centof sulfur trioxide.

Example3 (H) NH: (3 11 -SO H 0 SOsH N N 0 II I I II NHC CNH 0 sulfuricacid containing 28 per 100 parts of ice are added to a solution of 18.5parts of cyanuric chloride in parts of acetone. To the resultingsuspension of cyanuric chloride there is added a solution, cooled to 0C., of 19.5 parts of the sodium salt of 1-amino-benzene-3-su1fonic acidin 300 parts of water. There are immediately added dropwise to themixture 55 parts by volume of a 2 N-solution of sodium carbonate, the pHvalue being maintained between 5.0 and 7.0 and the temperature beingmaintained at 0-4" C. by external cooling. There is obtained a clearsolution of the primary condensation product of equimolecular quantitiesof cyanuric chloride and l-amino-benzene-3-sulfonic acid, that is tosay, a solution of 2:4-dichloro-6-phenylamino-1:3 :5-triazine-3'-sulfonic acid.

To the solution so obtained is then added a solution at 70 C. of 34parts of sodium 1:5-diaminoanthraquinone-Z-sulfonate in 1000 parts ofWater, and there are gradually added at 65-70" C. 55 parts by volume ofa 2 N-solution of sodium carbonate so as to maintain the pH valuebetween 5.0 and 7.0 Towards the end the mixture is stirred for one hourat 65 C., the pH value remaining constant between 6.5 and 7.0. Thedyestufi is then precipitated from the solution in the form of fineneedles by the addition of sodium chloride, and filtered off after beingcooled. The filter residue is washed with a soduim chloride solution of20% strength and the dyestutf is dyed in vacuo at 70 C.

Cotton or regenerated cellulose is dyed with the dyestulf by theprocedure described in Example 1 to give redorange tints which are very'fast to washing, chlorine and light.

100 parts of ice are added to a solution of 18.5 parts of cyanuricchloride in 80 parts of acetone. To the resulting fine suspension ofcyanuric chloride is added a solution, cooled to C. of 19.5 parts of thesodium salt of 1- aminobenzene-4-sulfonic acid in 300 parts of water. 55parts by volume of a 2 N-solution of sodium carbonate are thenimmediately run in such manner as to maintain the pH value between 5.0and 7.0. The temperature is maintained between 0 and 4 C. by externalcooling. Towards the end the suspension of the2:4-dichloro-6-phenylaminol:3:5-triazine-4'-sulfonic acid whichprecipitates in the form of colorless crystals, is heated to 40 C., anda solution at 70 C. of the sodium salt of 34 parts of1:4-diaminoanthraquinone-2-sulfonic acid in 1000 parts of water isadded. There are also added gradually dropwise at 60-65 C. 55 parts byvolume of a 2 N-solution of sodium carbonate at a pH value of 5.5 to7.0. After being stirred for further 30 minutes at 65 C., the dyestuffis salted out with sodium chloride. It precipitates in hair-fineblue-violet needles which are filtered off, after cooling the mixture toroom temperature, and then washed with sodium chloride solution of 10%strength. The dyestuff can be dried in the usual manner at 7080 C. invacuo.

Cotton or regenerated cellulose are dyed by the procedure described inExample 1 blue-violet tints of very good fastness to light and washing.

Similar dyestufls are obtained by using in this Example instead of1-aminobenzene-4-sulfonic acid, l-aminoben zene-3-sulfonic acid orl-aminobenze-Z-sulionic acid or 2- aminonaphthalene-6-sulfonic acid orZ-aminonaphthalene- 4:8 disulfonic acid.

Example 5 A solution of -19 parts of cyanuric chloride in 80 parts ofacetone is added to a solution, cooled to 0 C. by the addition of ice,of 53.3 parts of the disodium salt of lamino-4(4-aminophenylamin0)-anthraquinone 2:5-disulfonic acid in 2000 parts ofwater. The reaction mixture is stirred for about 40 minutes at 0-5 C.,during which the pH value of the mixture is maintained between 5 and 7.5by the addition of a total of about 52 parts by volume of a 2 N-solutionof sodium hydroxide. The dyestuif formed is dissolved. A test portiondiluted with Water gives on filter paper a blue outspread which whendabbed with 2 N-acetic acid no longer shows a change of tint to red.After the addition of a solutionof 23.5 parts of the sodium salt of=1-hydroxybenzene-3-sulfonic acid in 300 parts of water, the reactionmixture is heated to 35-40 C. and stirred for 3 hours at thattemperature, during which the pH value is maintained between 7 and 8 bythe addition of a total of about 50 parts by volume of a 2 N-solution ofsodium hydroxide. The dyestuff formed is precipitated by the addition ofsodium chloride, filtered 01f and dried in vacuo at 90 C. It is a darkcolored substance which dyes cotton and regenerated cellulose by themethod described in Example 1 blue tints which are fast to washing andlight.

What is claimed is:

1. The water-soluble anthraquinone dyestuif of the formula 2. Thewater-soluble anthraquinone dyestuff of the formula N SI a $0111 3. Thewater-soluble dyestult of the formula References Cited in the file ofthis patent UNITED STATES PATENTS 11,625,530 Fritzsche et al. Apr. 19,1927 2,773,871 Brassel et al Dec. M, 1956 FOREIGN PATENTS 467,815 GreatBritain June 23, 1932 466,886 Great Britain June 4, 1937

1. THE WATER-SOLUBLE ANTHRAQUINONE DYESTUFF OF THE FORMULA